1. Field of the Invention
The invention relates to the catalytic oxidation of olefins to substituted dioxolanes, and more particularly relates to the catalytic oxidation of olefins to substituted dioxolanes over molybdenum catalysts.
2. Other Methods in the Field
The reaction of unsaturated hydrocarbons or olefins with oxygen to produce olefin oxides or alkane epoxides is well known. Such a reaction is even known to occur non-catalytically. See, for example, U.S. Pat. No. 4,380,659 to Solomon which teaches olefin oxidation in the presence of a methyl formate solvent.
However, most of the procedures involve the use of a catalyst. U.S. Pat. No. 3,957,690 discloses a heterogeneous catalyst for the direct oxidation of propylene which may involve oxides of one or more of the following elements: scandium, yttrium, indium, gallium, thallium, rare earth elements of the lanthanide group, silver, vanadium, molybdenum, tungsten, bismuth, manganese and tantalum.
Olefins having four carbon atoms, the butenes, have also been paid much attention. For example, D. J. Hucknall in Selective Oxidation of Hydrocarbons, Academic Press: New York, 1974, pp. 96-97, teaches that the oxidation of butenes to carbonyl compounds is known to occur over such catalysts as copper(I) oxide, SnO.sub.2 --MoO.sub.3 and Co.sub.3 O.sub.4 --MoO.sub.3. A process for the oxidation of butenes and isobutylene in the presence of trivalent cobalt and a carbonyl compound is taught in European patent application 41,726. The liquid phase oxidation of lower olefins such as 1-butene and 2-butene in the presence of no catalyst, azobisisobutyronitrile, calcium oxide, cobaltic acetylacetonate, cobalt naphthenate, magnesium oxide and mixtures thereof was explored by W. F. Brill, et al. in "The Liquid Phase Oxidation of the Lower Olefins," J. Org. Chem., Vol. 29, 1964, pp. 140-143. U.S. Pat. No. 4,390,738 reveals a process for the oxidation of olefinic compounds (especially those with 2-4 carbons) to olefin oxides or derivatives thereof in the presence of a catalyst containing copper bonded to a peroxy group.
Higher molecular weight olefins may also be oxidized catalytically as seen in F. F. Mayo, et al., "Oxidation of Organic Compounds," Vol. I (Advances in Chemistry Series 75), Amer. Chem. Soc., Washington, DC, 1968, pp. 78-92, where C.sub.15 to C.sub.18 .alpha.-olefin oxidations are taught. Trialkyl ethylene hydrocarbons may be oxidized with the salt of a heavy metal of Groups VI and VIII of the Periodic Table, such as cobalt naphthenate, cobalt stearate, cobalt acetate, cobalt toluate, manganese naphthanate, manganese acetate, ferrous naphthenate, ferrous acetate, ferrous phthalocyanine and mixtures thereof according to U.S. Pat. No. 3,007,944 to Amir. British Pat. No. 1,483,354 discloses a process for the catalytic oxidation of an acyclic or cyclic mono- or diolefin with oxygen to form epoxy-alcohols in the presence of organovanadium complexes. Similarly, cyclic olefins are oxidized in the presence of vanadium complexed with acetylacetonate and azobisisobutyronitrile using the methods of K. Kaneda, et al., "Direct Epoxy Alcohol Synthesis from Cyclic Olefins Using O.sub.2 and VO(acac).sub.2 -AlBN Catalyst System," J. Org. Chem. (1980), Vol. 45, pp. 3004-3009.
Further, S. Ito, et al. of "[Fe.sub.3 O(OCOR).sub.6 L.sub.3 ].sup.+ -Catalyzed Epoxidation of Olefinic Alcohol Acetates by Molecular Oxygen," J. Amer. Chem. Soc. (1982), Vol. 104, pp. 6450-6452, teach the oxidation of complicated olefins in the presence of iron complex catalysts. 1-Octene, neat or in tetrachloroethane, reacts with oxygen in the presence of cyclic adducts of peroxobis(triphenylphosphine) platinum with carbon dioxide or hexafluoroacetone to produce the expected autoxidation products and 2-octanone as revealed by W. F. Brill, "Carbon Dioxide and Hexafluoroacetone Adducts of Peroxobis(triphenylphosphine) platinum in the Oxidation of 1-Octene," J. Molecular Catalysis (1983), Vol. 19, pp. 69-79.
In particular, molybdenum compounds have attracted attention as catalysts. Note the use of molybdyl-(V)-octaethylporphyrin-hydroxide in the article by M. Baccouche, et al. entitled, "Metallo-porphyrin Catalysed Epoxidations with Molecular Oxygen," J.C.S. Chem. Comm. (1977), pp. 821-822. A. F. Noels, et al., "Homogeneous Catalysts by Transition Metal Complexes. Selective Oxidation of Cyclohexene by Mixed-Catalysts Containing Rhodium(II) Complexes," J. Organometallic Chemistry, Vol. 166 (1979), pp. 79-86, reveal the oxidation of cyclohexene in the presence of molybdenum acetylacetonate and molybdenum hexacarbonyl.
Lower olefins such as propylene may also be oxidized in the presence of various molybdenum catalysts, such as CoMoO.sub.4.V.sub.2 O.sub.5, Sn/Mo oxides, Sn/Mo/Fe oxides among others as taught by T. G. Alkhazov, et al. in "Catalytic Oxidation of Propylene," Russian Chem. Reviews, (1982), Vol. 51, No. 6, pp. 542-551. J. Rouchaud, et al. in "Structure et Activite Catalytique Epoxydante des Chelates du Cation Molybdyle," Bulletin de la Societe Chimique de France (1969), No. 7, pp. 2294-2295, reveals the oxidation of propylene in the presence of molybdenum chelates. Several azo-compound chelates of MoO.sub.2.sup.2+, Wo.sub.2.sup.2+, Co.sup.2+, Cr.sup.3+ and Cu.sup.2+ were used as catalysts in the oxidation of propylene by molecular oxygen according to J. Rouchaud, et al. in "Catalysis by Chelates of Transition Elements of the Liquid Phase Oxidation of Propylene," J. of Catalysis (1970), Vol. 19, pp. 172-175. See also the use of molybdenum catalysts for the direct oxidation of propylene by J. E. Lyons, "Up Petrochemical Value by Liquid Phase Catalytic Oxidation," Hydrocarbon Processing, (November 1980), pp. 107-119, especially page 117 which teaches MoO.sub.5, Mo(acetylacetone).sub.3 and MoO.sub.2 (acetylacetonate).sub.2.
Higher olefins are also known to be oxidized using molybdenum catalysts. For example, MoO.sub.2 (acetylacetonate).sub.2 and MoO.sub.2 are used to catalyze the oxidation of octene in D. Rothe, et al., "Uber die Katalysierte Flussigphasen Oxidation von cis- und trans-Oct-4-en," J. Prakt. Chemie (1982), Vol. 324, No. 4, pp. 596-608. Dicyclopentadiene is oxidized over similar catalysts in D. Schnurpfeil, "Katalysierte Flussigphasenoxidation von Dicyclopentadine," J. Prakt. Chemie (1983), Vol. 325, No. 5, pp. 842-847.
The compound used as catalyst in this invention, molybdenum 8-hydroxyquinoline, is well known, but not as a catalyst. 8-Hydroxyquinoline has been studied extensively as an extracting agent, such as to recover molybdenum from sea water. See, for example, Chem. Abstracts 100:150025(18), 97:200304(24), 91:145812(18) and 70:14899 (4).
No literature references are known for the direct synthesis of dioxolanes from simple olefins, such as propylene and 2-butene.